1. Field of the Invention
This invention relates to a process and the resultant composition whereby a lower alkene monomer is converted to a lower alkene polymer through the use of unique reaction conditions and catalyst system. The lower alkene polymers so obtained have a high degree of mono-unsaturation content and are highly reactive in various reactions.
2. Description of the Art Practices
It is known from U.S. Pat. No. 2,816,944 issued Dec.17, 1957 to Muessig et al that olefinic polymers ranging in a carbon content of from 12 to 50 carbon atoms obtained from olefins having 5 to 25 carbon atoms may be prepared by using boron trifluoride with phosphoric acid. It is generally disclosed by Muessig et al that the polymerization may take place using kieselguhr, and is conveniently conducted at a temperature of 35.degree. C. to 60.degree. C.
Serniuk in U.S. Pat. No. 2,810,774 issued Oct. 22, 1957 describes an olefin polymerization catalyst system comprising boron trifluoride and acids of phosphorus. It is also disclosed by Serniuk that various absorbents such as aluminum silicates, kieselguhr, Fuller's earth, clays and silica gel may be employed as a support system for the catalyst. The Serniuk reference describes reaction temperatures of 77.degree. F. (24.degree. C.) to 212.degree. F. (100.degree. C.) during the polymerization. The olefins of Serniuk include a mixed propylene-butylene system having an active content of about 40% olefins.
U.S. Pat. No. 2,976,338 issued Mar. 21, 1961 to Thomas discloses a catalyst system comprising boron trifluoride and phosphoric acid as being too active for polymerizing olefins because of the rapid evolution of heat. It is disclosed that the boron trifluoride of Thomas may be modified through the inclusion of a potassium acid fluoride salt to give an acceptable product. The olefins employed by Thomas include from 5 to 15 carbon olefins for use in obtaining polymers containing from 10 to 30 carbon atoms. The reaction temperatures of the Thomas patent are generally in range of 32.degree. F. (0.degree. C.) to 212.degree. F. (100.degree. C.), preferably from 100.degree. F. (38.degree. C) to 160.degree. F. (71.degree. C.).
It is known from the U.S. Pat. No. 2,416,106 issued Feb. 18, 1947 to Linn et al that olefins may be polymerized through the combination of boron fluoride and an acid fluoride metal. U.S. Pat. No. 2,585,867 to Sparks et al issued Feb. 12, 1952 describes the production of high molecular weight polymers from monomers using a boron trifluoride catalyst system with reaction temperatures from -40.degree. C. to -103.degree. C. In particular, Sparks is concerned with the reaction of mono-olefins with di-olefins.
Blewett in U.S. Pat. No. 4,469,910 issued Sept. 4, 1984 describes a process whereby a dimer fraction is reacted in an oligomerization process with an alpha-olefin in the presence of a phosphoric acid- modified boron tri-fluoride catalyst system. The Blewett reference is particularly concerned with the use of 6 to 12 carbon dimers obtained from the monomer which corresponds to the alpha-olefin. The oligomerization is conducted at from 5.degree. C. to 75.degree. C. U.S. Pat. No. 3,985,822 issued Oct. 12, 1976 to Watson describes the production of poly-n-butenes using aluminum chloride as a catalyst and employing a reaction temperature of 65.degree. F. (18.degree. C.) to 115.degree. F. (46.degree. C.).
U.S. Pat. No. 4,407,731 to Imai issued Oct. 4, 1983 describes catalytic compositions, useful in oligomerization and alkylation reactions, prepared by treating a metal oxide support such as aluminum with an aqueous solution of an acid. One of the catalysts suggested for use in the support system of Imai is boron fluoride. U.S. Pat. No. 4,429,177 to Morganson et al issued Jan. 31, 1984 describes obtaining an alpha-olefin polymer in the presence of a 3 component catalyst system comprising a solid absorbant, boron trifluoride and elemental oxygen. U.S. Pat. No. 1,885,060 issued Oct. 25, 1932 to Hofmann et al describes using boron fluoride as a catalyst for propylene or butylene. It is also disclosed that various hydrogen halides may also be utilized with the boron fluoride.
Schmurling et al U.S. Pat. No. 2,369,691 issued Feb. 20, 1945 describes the use of sulfuric acid and metal halides of the Friedel-Crafts type. The catalyst system is stated to be useful in the isomerization of saturated hydrocarbons, the alkylation of cyclic aliphatic hydrocarbons, and in the polymerization of unsaturated hydrocarbons. U.S. Pat. No. 2,404,788 issued July 30, 1946 to Burk et al discloses various aluminate or silicate support systems for boron trifluoride.
U.S. Pat. No. 4,400,565 issued to Darden et al Aug. 23, 1983 describes oligomerizing olefins in the presence of boron trifluoride and a co-catalyst comprising a heterogeneous cationic ion exchange resin. U.S. Pat. No. 2,442,645 to Elwell et al issued June 1, 1948 describes the polymerization of normal lower mono-olefins which are dissolved in liquid sulfur dioxide. The reaction according to Elwell is carried out in the presence of a boron fluoride catalyst.
U.S. Pat. No. 2,406,869 to Upham issued Sept. 3, 1946 describes the preparation of an olefin polymerization catalyst comprising boron trifluoride and a hydrogen halide source. U.S. Pat. No. 2,199,180 to Laughlin which issued Apr. 30, 1940 describes the use of sulfuric acid and phosphoric acid for the polymerization of lower olefins. It is stated in Laughlin that it is desirable when treating the lower olefins to maintain the reaction temperature of above 200.degree. F. (95.degree. C.).
U.S. Pat. No. 2,536,841 issued Jan. 2, 1951 to Dornie describes the use of aluminum halides to polymerize olefins. The reaction temperatures suggested by Dornie are from 0.degree. C. to -164.degree. C. Dornie utilizes a low-freezing non-reacting solvent such as chloroform or sulfur dioxide in his process. U.S. Pat. No. 2,357,926 issued Sept. 12, 1944 to Bannon describes the use of boron fluoride and water for the polymerization of olefins.
U.S. Pat. No. 2,569,383 to Leyonmark et al issued Sept. 25, 1951 describes the polymerization of olefins from mono-olefins and polyolefins to give drying oils. U.S. Pat. No. 2,960,552 to Wasley issued Nov. 15, 1960 describes the use of methylchloride and boron trifluoride gas to polymerize lower olefins. U.S. Pat. No. 2,855,447 issued Oct. 7, 1958 to Griesinger et al describes an example of the polymerization of lower olefins through the use of hydrogen fluoride and boron trifluoride at temperatures of about 175.degree. F. (79.degree. C.). Bloch et al in U.S. Pat. No. 3,126,420 issued Mar. 24, 1964 describes the use of phosphoric acid and kielsguher to polymerize propylene at temperatures of 450.degree. F. (232.degree. C.) to 650.degree. F. (343.degree. C). The conditions for Bloch's reaction are from 600 to 1200 psi (4,100 KPa -8,100 KPa). Griesinger in U.S. Pat. No. 2,855,447 issued Oct. 7, 1958 discloses that olefins may be polymerized with boron trifluoride.
Perilstein in U.S. Pat. No. 3,749,560 issued July 31, 1973 describes the polymerization of a mixture of mono-olefins from C-12 and greater through the use of aluminum trichloride at temperatures of about 15.degree. C. to give polymers having a molecular weight of about 350 to about 1,500. Robert in U.S. Pat. No. 3,932,553 issued Jan. 13, 1976 discusses the polymerization of propylene in the presence of butadiene at 0.degree. C. to 60.degree. C. with boron trifluoride. Robert further discloses the use of phosphoric acid catalytic treatment of the di-olefin at from 130.degree. C. to 250.degree. C. British Patent No. 1,449,840 to Sanders published Sept. 15, 1976 describes the alkylation of benzene through the use of a Friedel-Crafts catalyst system.
It has been found in the present invention that a high vinylidene content polymer may be obtained by reacting a lower alkene monomer in the presence of a boron trifluoride and mineral acid catalyst system at about -3.degree. C. to about -30.degree. C. thereby giving an olefin polymer which is useful for producing an oil soluble composition. The olefin polymers of the present invention are highly reactive materials in that they contain a large degree of reactive mono-unsaturation.
Throughout the specification and claims percentages and ratios are by weight, temperatures are in degrees Celsius, and pressures are in KPa gauge unless otherwise indicated. Ranges and ratios utilized herein are illustrative and such may be combined to further describe the invention. It is also understood that mixtures of ingredients may be employed for each stated ingredient. The reference cited herein are, to the extent applicable, incorporated by reference for their disclosures.